KR20220161735A - Multilayer metal foils and fabricating method of the same - Google Patents

Abstract

The present specification relates to a multilayer metal thin film and a manufacturing method thereof. The multilayer metal thin film of the present invention comprises: a first plating layer; a metal layer containing copper formed on the upper surface of the first plating layer; a second plating layer formed on the upper surface of the metal layer; and a third plating layer formed on the upper surface of the second plating layer. The first plating layer, the metal layer, the second plating layer, and the third plating layer are sequentially plated on one cathode rotating plate by using an electroforming method.

Description

Multilayer metal foils and fabricating method of the same}

The present invention relates to a multilayer metal thin film independently electroformed and sequentially laminated on one cathode rotating plate and a method for manufacturing the same.

As the electronic device industry develops, demand for metal thin films used as a negative current collector in various circuit conductors and secondary batteries is increasing. Among them, copper foil has the advantage of being excellent in electrical characteristics compared to its price, so it is in the spotlight as a main material for PCB metal sheets used in printed circuit boards (PCBs), especially smart phone built-in antenna terminals.

Typically, the copper foil deposits an electrodeposited copper foil by immersing a drum coated with titanium on the surface and an insoluble cathode material acting as an anode in an electrolyte solution, and rotating the drum in one direction while current is applied to the drum and the cathode material. It is manufactured by an electroforming method, and a multilayer metal thin film is manufactured by coating nickel (Ni), gold (Au), etc. on the electrodeposited copper foil manufactured by the above method.

In fact, Korean Patent Registration No. 10-1991922 discloses a method of sputtering a metal protective layer and a gold (Au) layer on copper foil, and Korean Patent Registration No. 10-1150400 discloses an electroless plating method, a hot-dip plating method, A method of forming a multilayer thin film by an electrolytic plating method, a sputtering method, a chemical vapor deposition method, or the like is disclosed.

However, the method presented in the above-mentioned documents has a limitation in reducing the thickness of the copper foil, and there is a disadvantage in that it is difficult to manufacture a metal thin film of 20 μm or less, and folding and tearing occur in the process of plating the previously prepared copper foil. The downside is that productivity may decrease.

In addition, in the above method, the bonding force between the copper foil and the metal layer plated thereon is weak, and additional heat treatment must be performed to compensate for this.

For this reason, there is a demand for a multi-layer metal thin film and a manufacturing method thereof capable of freely adjusting the thickness of the copper foil and securing bonding strength without additional heat treatment.

Republic of Korea Patent Registration No. 10-1991922 (2019.06.17.) Republic of Korea Patent No. 10-1150400 (2012.05.21.)

In order to solve the above problems, the present invention can provide a multi-layer metal thin film and a manufacturing method in which a first plating layer, a metal layer, a second plating layer, and a third plating layer are sequentially stacked on one cathode rotating plate.

One embodiment of the present invention for achieving the above object is a first plating layer, a metal layer containing copper formed on the upper surface of the first plating layer, a second plating layer formed on the upper surface of the metal layer, and a third plating layer formed on the upper surface of the second plating layer. Including, the first plating layer, the metal layer, the second plating layer and the third plating layer are sequentially plated on one cathode rotating plate using an electroforming method, it relates to a multi-layer metal thin film.

In the above embodiment, the multi-layer metal thin film may be manufactured by a multi-layer metal thin film manufacturing apparatus including the cathode rotating plate and first to fourth electrolytic cells electroforming with the cathode rotating plate.

In the above embodiment, the first to fourth electrolytic cells are disposed spaced apart from each other by a predetermined distance on one of the cathode rotating plates, and as the cathode rotating plate rotates, the first to fourth electrolytic cells are connected to the cathode rotating plate. It can be electroformed at the same time.

In the above embodiment, the first plating layer and the second plating layer are any one metal selected from the group consisting of nickel (Ni), cobalt (Co), tin (Sn), zinc (Zn), and iron (Fe). can be made with

In the above embodiment, the thickness of the first plating layer may be formed to be 0.5 to 5 μm, and the thickness of the second plating layer may be formed to be formed to be 1 to 10 μm.

In the above embodiment, the metal layer may be provided as an electrolytic copper foil layer.

In the above embodiment, the third plating layer may be made of any one metal among gold (Au), silver (Ag), palladium (Pd), platinum (Pt), and aluminum (Al).

Another embodiment of the present invention is a method for manufacturing a multi-layer metal thin film in which a first plating layer, a metal layer, a second plating layer, and a third plating layer are sequentially plated on a cathode rotating plate, the step of charging the cathode rotating plate on the upper surface of the cathode rotating plate Forming a first plating layer on the top surface of the first plating layer, forming a metal layer on the top surface of the first plating layer, forming a second plating layer on the top surface of the metal layer, forming a third plating layer on the top surface of the second plating layer, and manufacturing multi-layer Manufacturing of a multi-layer metal thin film comprising the step of peeling off the metal thin film, wherein as the cathode rotating plate rotates, the first plating layer, the metal layer, the second plating layer and the third plating layer are simultaneously electroformed. It's about how.

In the above embodiment, a step of sealing the metal thin film may be further included between the step of forming the third plating layer and the step of peeling the multi-layer metal thin film.

In the above embodiment, the multi-layered metal thin film may include the cathode rotating plate and first to fourth electrolytic cells that are electroformed with the cathode rotating plate.

In the above embodiment, the first plating layer is formed by spraying a first electrolyte into the first electrolytic cell and then passing a first current, and the first cathode material included in the first electrolytic cell has solubility. It can be provided as a nickel (Ni) metal plate with

In the above embodiment, the metal layer is formed by spraying a second electrolyte into the second electrolytic cell and then passing a second current, and the second cathode material included in the second electrolytic cell has solubility. It may be provided as a copper (Cu) metal ball.

In the above embodiment, the third plating layer is formed by spraying a fourth electrolyte into the fourth electrolytic cell and then passing a fourth current, and the fourth anode material included in the fourth electrolytic cell is iridium. It may be a titanium (Ti) plate coated with oxide (Ir ₂ O ₃ ).

Through this, the present invention simplifies the production process by sequentially stacking the first plating layer, the metal layer, the second plating layer, and the third plating layer on one cathode rotating plate, prevents folding and tearing of the copper foil during the plating process, and separate Sufficient strength can be secured without heat treatment.

In addition, the present invention provides the second cathode material as a soluble copper (Cu) metal ball, thereby preventing oxygen gas from being generated during the formation of the metal layer, thereby improving the quality of the metal layer. .

1 is a view for explaining a process of manufacturing a multilayer metal thin film used for a printed circuit board (PCB) using a conventional electrodeposited copper foil and an antenna terminal for communication.
2 is a view for explaining a multi-layer metal thin film manufacturing apparatus according to an embodiment of the present invention.
3 is a view for explaining a multi-layer metal thin film according to an embodiment of the present invention.
4 is a flowchart illustrating a method of manufacturing a multi-layer metal thin film according to an embodiment of the present invention.
5 is a diagram for explaining step S20 according to an embodiment of the present invention.
6 is a diagram for explaining step S30 according to an embodiment of the present invention.

Hereinafter, a multilayer metal thin film and a manufacturing method thereof according to the present invention will be described in detail. The drawings introduced below are provided as examples so that the spirit of the present invention can be sufficiently conveyed to those skilled in the art. Therefore, the present invention may be embodied in other forms without being limited to the drawings presented below, and the drawings presented below may be exaggerated to clarify the spirit of the present invention. At this time, unless there is another definition in the technical terms and scientific terms used, they have meanings commonly understood by those of ordinary skill in the art to which this invention belongs, and the gist of the present invention in the following description and accompanying drawings Descriptions of known functions and configurations that may unnecessarily obscure are omitted.

One feature of the present invention relates to a multilayer metal thin film, which is a raw material of a printed circuit board (PCB) or a metal sheet used for the printed circuit board, on which electronic components and wiring related thereto are mounted.

More preferably, it relates to a multilayer metal thin film in which a first plating layer and a second plating layer are formed on both surfaces of a metal layer containing copper, and a third plating layer is formed on an upper surface of the second plating layer.

Typically, the multi-layer metal thin film is a step of pre-treating a pre-produced electrodeposited copper foil or rolled copper foil (hereinafter referred to as copper foil) through a cathode drum as shown in FIG. 1 (P10). Plating a plating layer containing nickel, cobalt (Co), arsenic (As), tungsten (W), chromium (Cr), zinc (Zn), phosphorus (P) and manganese (Mn) on both sides of the pretreated copper foil steps (P20, P30); The multilayer metal thin film 100 may be manufactured by sequentially proceeding to plating a metal layer including gold (Au) on the plating layer (P40).

However, in the above method, a very thin copper foil having a thickness of 15 μm or less is required to reduce the thickness of the multilayer metal thin film to 20 μm or less. In the process of plating the metal layer, folding and tearing occur, resulting in very low productivity.

In addition, in the above method, the bonding force between the copper foil and the metal layer plated thereon is weak, and additional heat treatment must be performed to compensate for this.

In order to improve this, the present invention configures a cathode rotating plate 200 having an endless plate ring structure by welding a plurality of titanium plates as shown in FIG. 2, and electrocasting independently of the cathode rotating plate 200 A multi-layer metal thin film manufacturing apparatus 1000 including a plurality of electroforming cells 300 was configured.

According to an embodiment, the plurality of electrolytic cells 300 may include first to fourth electrolytic cells. In addition, the first to fourth electrolytic cells may be disposed spaced apart from each other by a predetermined distance on one cathode rotating plate 200, and as the cathode rotating plate rotates, the first to fourth electrolytic cells may be simultaneously disposed with the cathode rotating plate. It can be electroformed.

Through the multi-layer metal thin film manufacturing apparatus 1000, the multi-layer metal thin film 100 can be manufactured by sequentially plating the first plating layer, the metal layer, the second plating layer, and the third plating layer on the same cathode rotating plate 200.

In the multilayer metal thin film 100 according to an embodiment of the present invention, the step of charging the cathode rotating plate 200 (S10), after spraying the first electrolyte solution between the cathode rotating plate 200 and the first cathode material 410a, , supplying a first current to form a first plating layer on the upper surface of the cathode rotating plate 200 (S20), and applying a second electrolyte solution between the cathode rotating plate 200 and the second anode 410b material on which the first plating layer is formed. After spraying, supplying a second current to form a metal layer on the upper surface of the first plating layer (S30), spraying a third electrolyte solution between the cathode rotating plate 200 and the third anode material 410c on which the metal layer is formed , Forming a second plating layer on the upper surface of the metal layer by supplying a third current (S40), spraying a fourth electrolyte between the cathode rotating plate 200 and the fourth anode material 410d on which the second plating layer is formed, It may include forming a third plating layer on the upper surface of the second plating layer by supplying a fourth current (S50), and peeling the manufactured multilayer metal thin film (S60). A detailed description of each manufacturing method will be described later.

That is, the multi-layer metal thin film manufacturing apparatus 1000 according to an embodiment of the present invention shares one cathode rotating plate 200 rotating in one direction, and a plurality of anode materials 410a that are electroformed with the cathode rotating plate 200. , 410b, 410c, 410d...; 410) may be included. With this feature, the multi-layer metal thin film manufacturing apparatus 1000 can form a multi-layer metal thin film with one device by electroforming the cathode rotating plate 200 and the plurality of anode materials 410 independently. can

At this time, each cathode material 410 may be included inside the electrolysis cell 400 .

For example, the first cathode material 410a may be included in the first electrolysis cell 400a. In addition, the first electrolytic cell 400a may include a first electrolyte solution supply nozzle 430a for spraying a first electrolyte solution between the cathode rotating plate 200 and the first cathode material 410a.

In other words, the first electrolytic cell 400a may include the first positive electrode material 410a and the first electrolyte supply nozzle 430a therein. Through this, the first electrolytic cell 400a supplies electrolyte into the first electrolytic cell 400a through the first electrolyte supply nozzle 430a, and the cathode rotating plate 200 and the first cathode material ( 410a), the first electrolyte solution may be injected.

Although the configuration and role of the first electrolysis cell 400a has been described above, it is not limited thereto and can be equally applied to the second electrolysis cell 400b, the third electrolysis cell 400c, and the fourth electrolysis cell 400d. have. In addition, in the present specification, it has been described that the multi-layer metal thin film is manufactured through the first to fourth electrolysis cells, but it is not limited thereto, and it is possible to manufacture a multi-layer metal thin film by combining more electrolysis cells. self-explanatory

That is, the multilayer metal thin film manufacturing apparatus 1000 according to an embodiment of the present invention simplifies the production process by performing the process of manufacturing copper foil and the process of forming a plating layer on the manufactured copper foil at once using one device. In addition, it is possible to improve productivity by preventing folding and tearing of the copper foil during the plating process. In addition, since there is no need to use pre-manufactured copper foil as a raw material, it is of course possible to solve the problem of management of raw materials and defects.

In addition, the multilayer metal thin film manufacturing apparatus 1000 according to an embodiment of the present invention provides a cathode material on which a metal layer containing copper (Cu) is formed as a copper (Cu) metal ball having a solubility, so that the metal layer It is possible to prevent the generation of oxygen gas during the formation process. Through this, the quality of the metal layer can be improved.

In addition, the multilayer metal thin film manufacturing apparatus 1000 according to an embodiment of the present invention independently provides process conditions such as the type, concentration, and current density of the electrolyte solution supplied to each electrolysis cell in the plurality of electrolysis cells 300. By doing so, the electrical, physical and mechanical properties of the metal thin film can be diversified. Through this, single- or multi-layer metal thin films can be manufactured, and electrical, physical and mechanical properties can be diversified according to each part of the metal thin film.

The characteristics of the multi-layer metal thin film manufacturing apparatus according to the embodiment of the present invention have been described above. Hereinafter, a multilayer metal thin film according to an embodiment of the present invention will be described with reference to FIG. 3 .

3 is a view for explaining a multi-layer metal thin film according to an embodiment of the present invention.

Referring to FIG. 3 , the multilayer metal thin film 100 according to an embodiment of the present invention may include a first plating layer 110, a metal layer 130, a second plating layer 150, and a third plating layer 170. .

According to the embodiment, the first plating layer 110, the metal layer 130, the second plating layer 150, and the third plating layer 170 are electroformed by one cathode rotating plate, and the same cathode rotating plate The first plating layer 110 , the metal layer 130 , the second plating layer 150 , and the third plating layer 170 may be plated in this order.

According to the embodiment, the cathode rotating plate refers to a ring-shaped rotating plate charged with a negative electrode, and more preferably, a plurality of titanium plates are welded in one direction, and both ends of the connected titanium plates are connected to a ring ( Refers to a rotating plate welded in the shape of a ring. That is, the cathode rotating plate may be provided in the form of an endless plate ring by welding a plurality of titanium plates.

The first plating layer 110 is made of a metal other than copper (Cu), and more preferably, can be provided as a metal plating layer that is relatively inexpensive compared to copper (Cu) and has excellent tensile strength and mechanical reliability. have. Through this, it is possible to protect the metal layer 130 including copper (Cu), which will be described later.

According to an embodiment, the first plating layer 110 is any one selected from the group consisting of nickel (Ni), cobalt (Co), tin (Sn), zinc (Zn), and iron (Fe) and iron (Fe). It may be provided as a metal or an alloy containing the same. Hereinafter, in the present specification, the first plating layer is described as a nickel (Ni) plating layer, but is not limited thereto.

According to an embodiment, the thickness of the first plating layer 110 is preferably provided in a range of 0.5 to 5 μm. If the thickness of the first plating layer 110 is less than 0.5 μm, the ability of the first plating layer 110 to protect the metal layer 130 may be reduced and the metal layer 130 may be damaged. Conversely, if the thickness of the first plating layer 110 exceeds 5 μm, the adhesive strength between the first plating layer 110 and the metal layer 130 is lowered, causing a defect in which a portion of the first plating layer is peeled off during use. can For this reason, the thickness of the first plating layer 110 is preferably 0.5 to 5 μm, more preferably 0.3 to 3 μm.

The metal layer 130 is a metal layer containing copper (Cu), more preferably an electrolytic copper foil, a rolled copper foil, or It may be made of battery copper foil. Hereinafter, in the present specification, an example in which the metal layer 130 is provided as an electrolytic copper foil layer is described, but is not limited thereto.

According to the embodiment, the metal layer 130 may be formed by electroforming on the cathode rotating plate on which the first plating layer 110 is formed. That is, the metal layer 130 may be formed through the same negative electrode plate as the negative electrode plate on which the first plating layer 110 is formed. In this process, since the metal layer 130 is formed on the first plating layer 110 through electroforming without using a physical method such as sputtering, the first plating layer 110 or the metal layer 130 damage can be minimized.

In addition, since the metal layer 130 is directly formed on the upper surface of the first plating layer 110 through electroforming, there is an advantage in that a separate bonding process such as soldering or heat treatment is not required to improve bonding strength. .

According to an embodiment, the thickness of the metal layer 130 is preferably provided to 5 to 30㎛. When the thickness of the metal layer 130 is less than 5 μm, mechanical properties of the metal layer 130 may be excessively reduced. This may cause cracks or deformation when additionally plating the second plating layer 150 or the third plating layer 170 on the metal layer. On the other hand, when the thickness of the third plating layer 130 exceeds 30 μm, the thickness of the multi-layer metal thin film 100 increases excessively, and thus the usability may decrease. For this reason, the metal layer 130 may have a thickness of 5 to 30 μm, more preferably 8 to 15 μm.

The second plating layer 150 may be formed on the metal layer 130 and, like the first plating layer 110 and the metal layer 130, may be formed by electroforming on the same cathode rotating plate. That is, the first plating layer 110, the metal layer 130, and the second plating layer 150 may be sequentially plated by the same cathode rotating plate.

According to an embodiment, like the first plating layer 130, the second plating layer 150 may be provided as a metal plating layer superior in tensile strength and mechanical reliability to copper (Cu). Through this, the metal layer 130 can be protected.

According to the embodiment, the second plating layer 150, like the first plating layer 110, is made of nickel (Ni), cobalt (Co), tin (Sn), zinc (Zn), and iron (Fe). It may be provided as any one selected metal or an alloy containing the same. Hereinafter, in the present specification, the second plating layer is described as a nickel (Ni) plating layer, but is not limited thereto.

According to the embodiment, the second plating layer 150 is formed between the metal layer 130 and the third plating layer 170 to be described later to improve bonding strength between the metal layer 130 and the third plating layer 170. At the same time, it is possible to prevent components such as gold (Au) included in the third plating layer 170 from penetrating into the metal layer 130 . For this reason, it is preferable that the second plating layer 150 is thicker than the first plating layer 110 .

Specifically, the second plating layer 150 preferably has a thickness of 1 to 10 μm. If the thickness of the second plating layer 150 is less than 1 μm, the ability to protect the metal layer 130 may decrease, and components such as gold (Au) included in the third plating layer 170 may reduce the metal layer 130 thickness. (130), the electrical properties may be reduced. On the other hand, when the thickness of the second plating layer 150 exceeds 10 μm, bonding strength between the metal layer 130 and the third plating layer 170 may decrease. For this reason, the thickness of the second plating layer 150 is preferably 1 to 10 μm, more preferably 5 to 8 μm.

Finally, the third plating layer 170 is formed on the third plating layer 150, and is electroformed on the same cathode rotating plate as the first plating layer 110, the metal layer 130, and the second plating layer 150. ) can be formed. That is, the first plating layer 110 and the metal layer 130. The second plating layer 150 and the third plating layer 170 may be sequentially plated by the same cathode rotating plate.

According to the embodiment, the third plating layer 170 is made of gold (Au), silver (Ag), palladium (Pd), platinum (Pt), chromium (Cr), titanium (Ti), niobium (Nb), tungsten (W ), may be composed of any one metal selected from the group consisting of molybdenum (Mo) and aluminum (Al) or an alloy containing the same. Hereinafter, in the present specification, it is described as including gold (Au) as an example, but is not limited thereto.

According to the embodiment, a wiring or component for a printed circuit board (PCB) may be mounted on the upper surface of the third plating layer 170 .

According to an embodiment, the thickness of the third plating layer 170 is preferably provided in a range of 0.02 to 0.1 μm. If the thickness of the third plating layer 170 is less than 0.02 μm, it is difficult to implement electrical characteristics, and if the thickness of the third plating layer 170 exceeds 0.1 μm, the production cost increases and the quality of the third plating layer 170 increases. The bond may be weakened and peeling may occur. For this reason, the thickness of the third plating layer 170 is preferably 0.02 to 0.1 μm, more preferably 0.05 to 0.08 μm.

The configuration of the multilayer metal thin film according to an embodiment of the present invention has been described through FIG. 3 above. Hereinafter, a method of manufacturing a multi-layer metal thin film according to an embodiment of the present invention will be described through FIGS. 4 to 6.

Figure 4 is a flow chart for explaining a method for manufacturing a multi-layer metal thin film according to an embodiment of the present invention, Figure 5 is a diagram for explaining step S20 according to an embodiment of the present invention, Figure 6 is an embodiment of the present invention It is a diagram for explaining step S30 according to.

Referring to FIG. 4, the multi-layer metal thin film according to an embodiment of the present invention is a multi-layer metal thin film including a cathode rotating plate and a plurality of electrolytic cells 300 for producing a specific metal thin film by electroforming independently of the cathode rotating plate. It can be manufactured by the manufacturing apparatus 1000, and more preferably, charging the cathode rotating plate (S10), spraying a first electrolyte solution between the cathode rotating plate and the first cathode material, and then supplying a first current Forming a first plating layer on the upper surface of the cathode rotating plate (S20), spraying a second electrolyte solution between the cathode rotating plate on which the first plating layer is formed and the second cathode material, and then supplying a second current to the upper surface of the first plating layer Forming a metal layer (S30), spraying a third electrolyte solution between the cathode rotating plate on which the metal layer is formed and the third anode material, and then supplying a third current to form a second plating layer on the upper surface of the metal layer (S40), Forming a third plating layer on the upper surface of the second plating layer by spraying a fourth electrolyte between the cathode rotating plate on which the second plating layer is formed and the fourth anode material, and supplying a fourth current (S50), and the manufactured multi-layer metal A step of peeling the thin film (S60) may be included.

According to an embodiment, as the cathode rotating plate rotates, the first plating layer, the metal layer, the second plating layer, and the third plating layer may be electroformed at the same time.

The step S10 is a step of charging the cathode rotating plate 200 with a cathode by supplying current to the cathode rotating plate 200 .

According to the embodiment, the cathode rotating plate 200 may receive current through a separately provided electrode unit (not shown). Through this, the cathode rotating plate 200 can be charged with a cathode.

Thereafter, the first plating layer 110 may be formed on the upper surface of the cathode rotating plate 200 through the step S20. Since the detailed description of the first plating layer 110 has been described above, it will be omitted.

According to the embodiment, in step S20 , the first plating layer 110 may be formed through electroforming of the cathode rotating plate 200 and the first anode material 410a.

Referring to FIG. 6 , the multilayer metal thin film manufacturing apparatus 1000 sprays a first electrolyte between the cathode rotating plate 200 and the first anode material 410a through the first electrolyte supply nozzle 430a. can Thereafter, the electrode unit may deposit a first plating layer 110 on the cathode rotating plate 200 by supplying a first current between the cathode rotating plate 200 and the first cathode material 410a.

According to the embodiment, the first electrolyte supply nozzle 430a continuously injects a larger amount of electrolyte than the electrolyte exposed through the gap between the cathode rotation plate 200 and the first electrolysis cell 400a to the cathode rotation plate. 200 and the first cathode material 410a may always be filled with the first electrolyte.

According to an embodiment, the first electrolyte solution is any one selected from nickel sulfamate (Ni(NH ₂ SO ₃ ) ₂ ), nickel sulfate (NiSO ₄ 6H ₂ O), and nickel chloride (NiCl ₂ ), or a mixture thereof. It may be used, more preferably nickel sulfamate (Ni(NH ₂ SO ₃ ) ₂ ) 400 to 500 g / ℓ, nickel chloride (NiCl ₂ ) 5 to 20 g / ℓ and boric acid (H ₃ BO ₃ ) 30 to 50 g / ℓ may be provided as a mixed solution.

According to an embodiment, the first positive electrode material 410a may be provided as a soluble nickel (Ni) metal plate.

According to an embodiment, the first current may be 10 to 50A per 1dm ² . When the first current is less than 10A per 1dm ² , the current supplied to the cathode rotating plate 200 is low and the first plating layer ¹¹⁰ cannot grow to a sufficient thickness. If it exceeds 20A, the first plating layer 110 may overgrow, and defects may be formed in the first plating layer 110 . For this reason, the first current may be 10 to 30A per 1dm ² , more preferably 15 to 25A per 1dm ² .

Thereafter, the metal layer 130 may be formed on the upper surface of the first plating layer 110 through the step S30 . Since the detailed description of the metal layer 130 has been described above, it will be omitted.

Referring to FIG. 6 , in step S30 , the metal layer 130 may be formed through electroforming of the cathode rotating plate 200 and the second anode material 410b.

Specifically, the multilayer metal thin film manufacturing apparatus 1000 may spray the second electrolyte between the cathode rotating plate 200 and the second cathode material 410b through the second electrolyte supply nozzle 430b. Thereafter, the electrode unit supplies a second current of 35 to 50 A per 1 dm ² between the cathode rotating plate 200 and the second cathode material 410b to deposit the metal layer 130 on the cathode rotating plate 200. can

According to the embodiment, the second electrolyte supply nozzle 430b, like the first electrolyte supply nozzle 430a, has more liquid than the electrolyte exposed through the gap between the cathode rotating plate 200 and the second electrolytic cell 400b. By continuously spraying a large amount of electrolyte, the cathode rotating plate 200 and the second positive electrode material 410b may always be filled with the second electrolyte.

According to an embodiment, the second electrolyte solution may be provided as a copper precursor solution unlike the first electrolyte solution described above, and more preferably, copper (Cu) ions are added to 100 to 200 g/ℓ of sulfuric acid (H ₂ SO ₄ ). 50 to 100 g/ℓ may be provided as a mixed solution. At this time, copper (Cu) ions may be prepared by dissolving coin wire scraps in a sulfuric acid solution.

According to an embodiment, the second cathode material may be provided in the form of a soluble metal ball or soluble metal plate, more preferably a soluble copper ball or soluble copper plate. (Copper plate).

In general, a conventional electrodeposited copper foil provides a cathode material as an insoluble material that does not dissolve in an electrolyte, and manufactures a thin film by applying an electric current while the cathode material and a cathode drum are immersed in the electrolyte.

However, in the above method, an excess of oxygen (O ₂ ) may be generated at the anode and a small amount of hydrogen (H ₂ ) at the cathode during the electrolysis process. Excessive oxygen (O ₂ ) generated from the anode may be attached to the surface of the electrodeposited copper foil to cause surface defects, and may weaken electrical characteristics by oxidizing a part of the electrodeposited copper foil.

To prevent this, the present invention provides the second cathode material 410b in the form of a copper ball or a soluble copper plate soluble in the second electrolyte to maximize the surface area in contact with the electrolyte. can make it That is, the present invention can prevent oxygen (O ₂ ) from being attached to the surface of the cathode material by dissolving the second cathode material 410b in the second electrolyte solution.

In addition, as electroforming proceeds between the cathode rotary plate 200 and the second cathode material 410b, as it dissolves in the second electrolyte solution, the user visually checks the remaining amount of the second cathode material 410b can be replaced In addition, the user can appropriately control the amount and direction of the flow rate of the second electrolyte solution after visually checking the remaining amount of the second cathode material 410b. Through this, there is an advantage in that it is easy to check the replacement cycle of the second cathode material 410b and optimize process conditions.

According to the embodiment, since the second cathode material 410b requires a relatively low voltage for the same ionization process compared to a conventional insoluble cathode material, the same effect can be achieved even with a small voltage. Due to these characteristics, the second cathode material 410b according to the embodiment of the present invention has the advantage of reducing power cost compared to conventional insoluble cathode materials.

In other words, in the multilayer metal thin film 100 according to the embodiment of the present invention, the first plating layer 110 is deposited on the cathode rotating plate 200 through the first anode material 410a containing nickel (Ni) and , The metal layer 130 may be deposited on the first plating layer 110 through the second anode material 410b provided as a soluble copper ball or a soluble copper plate.

That is, the multi-layered metal thin film 100 according to an embodiment of the present invention provides a cathode material, an electrolyte solution, and a current independently formed on the same cathode rotating plate 200 to manufacture multiple layers of metal thin films made of different materials on one cathode rotating plate. can do.

Thereafter, the second plating layer 150 may be formed on the upper surface of the metal layer 130 through the step S40 . Since the detailed description of the second plating layer 150 has been described above, it will be omitted.

According to the embodiment, in the step S40, the second plating layer 150 is electroformed ( Electroforming) may be formed. Since the third cathode material 430c, the third electrolyte solution, and the third current are identical to those of the first cathode material 410a, the first electrolyte solution, and the first current, a detailed description thereof will be omitted.

According to the embodiment, the number of electrolytic cells for plating the second plating layer 150 is the same as the number of electrolytic cells for plating the first plating layer 110, or electrolytic cells for plating the first plating layer 110. It can be plated by more electrolysis cells than the number. Through this, the second plating layer 150 can be plated to a thickness equal to or greater than that of the first plating layer 110 even when the same electrolyte conditions and the same amount of current are supplied as the first plating layer 110 .

Thereafter, the third plating layer 170 may be formed on the upper surface of the second plating layer 150 through the step S50 . Since the details of the third plating layer 170 have been described above, they will be omitted.

According to the embodiment, in the step S50, the third plating layer 170, like the first plating layer 110, the metal layer 130, and the second plating layer 150, the cathode rotating plate 200 and the fourth anode material It may be formed through electroforming of (430d).

According to an embodiment, the fourth electrolyte solution may be provided as a gold (Au) precursor solution unlike the first to third electrolyte solutions described above, more preferably, gold (Au) ions are 0.2 to 20 g / ℓ, nickel (Ni) ion can be provided as a mixed solution mixed with 700ppm.

According to the embodiment, the fourth positive electrode material 410d includes a first positive electrode material 410a and a third positive electrode material 410c provided as a metal plate of soluble nickel (Ni) or a soluble copper ball ( Unlike the second cathode material 410b provided as a copper ball, it may be provided as an insoluble cathode material, and more preferably as a titanium (Ti) plate coated with insoluble iridium oxide (Insoluble Ir ₂ O ₃ ). It can be.

This is because, when the fourth cathode material 410d is used as a soluble cathode material containing gold (Au), the manufacturing cost increases, but the effect difference is not large.

That is, the present invention deposits the first plating layer 110, the metal layer 130, the second plating layer 150, and the third plating layer 170 through anode materials of different materials, so that each layer is plated with a different metal. The metal thin film 100 can be manufactured.

Thereafter, through the step S60, electrical characteristics may be stabilized by sealing the multilayer metal thin film 100.

In the multilayer metal thin film 100, a large number of micropores may be formed in a metal layer or a plating layer during a manufacturing process. External contaminants may penetrate the metal thin film 100 through the micropores, contaminate the metal thin film, and cause corrosion. For this reason, it is possible to stabilize the electrical properties and prevent corrosion by sealing the multilayer metal thin film 100 .

As the sealing treatment method, a nickel acetic acid precipitation method may be applied, but is not limited thereto, and a hydration sealing method using boiling water or pressurized steam, a metal salt sealing method using metal salt, and an organic sealing method in which oil or organic materials are applied or deposited thereon. However, it is obvious that it can be performed by other disclosed methods, such as the painting sealing method by painting.

Finally, the multilayer metal thin film 100 may be peeled off from the cathode rotating plate 200 . According to the embodiment, the peeled multilayer metal thin film 100 may be peeled off from the cathode rotating plate 200 and then wound around a winding roll 600 provided in the metal thin film manufacturing apparatus 1000 and stored. have.

Although not disclosed in the drawing, a cleaning unit (not shown) may be included between the electrolytic cells 400 to remove foreign substances and residual electrolyte from the metal thin film. Through this, it is possible to remove foreign substances and residual electrolyte from the deposited surface of the metal thin film, and manage the surface evenly.

The manufacturing method of the multilayer metal thin film 100 according to the embodiment of the present invention has been described through FIGS. 4 to 6 above. In this specification, the multilayer metal thin film 100 has been described as an example of a metal thin film in which a first plating layer 110, a metal layer 130, a second plating layer 150, and a third plating layer 170 are sequentially stacked. It is not limited thereto, and it is obvious that the above or below metal layer may be included.

According to the embodiment of the present invention described above, the multi-layer metal thin film 100 is a first plating layer, a metal layer, a second plating layer, and a third plating layer through one cathode rotating plate and a plurality of anode materials electroformed with the cathode rotating plate. They can be stacked in this order.

According to an example, the multi-layer metal thin film 100 may be sequentially stacked on one cathode rotating plate 200 by supplying an anode material, an electrolyte, and current under the conditions shown in Table 1.

cathode material cathode material electrolyte electric current thickness 1st plating layer Ti Plate -Soluble
-Ni metal plate Ni(NH ₂ SO ₃ ) ₂ : 450g/ℓ
NiCl ₂ : 10g/ℓ
H ₃ BO ₃ : 35g/ℓ 20A/ ^dm2 3㎛ metal layer -Soluble
- Copper ball or
Copper plate H ₂ SO ₄ : 120g/ℓ
Cu ion: 80g/ℓ 45A/ ^dm2 12㎛ 2nd plating layer -Soluble
-Ni metal plate Ni(NH ₂ SO ₃ ) ₂ : 450g/ℓ
NiCl ₂ : 10g/ℓ
H ₃ BO ₃ : 35g/ℓ 20A/ ^dm2 7㎛ 3rd plating layer - Insoluble
-Ti plate coated
by Ir ₂ O ₃ Au ion: 2g/ℓ
Ni: 700ppm 1.5A/ ^dm2 0.08㎛

That is, the multilayer metal thin film 100 according to the embodiment of the present invention has the first plating layer 110, the metal layer 130, and the second plating layer 150 on one cathode rotating plate 200 according to the conditions disclosed in Table 1 above. ) and the third plating layer 170 may be sequentially stacked.

This simplifies the production process of the multilayer metal thin film, prevents folding and tearing of the copper foil in the plating process, and secures sufficient strength without additional heat treatment.

In fact, it was confirmed that the multilayer metal thin film 100 manufactured according to the embodiment of the present invention has a Vickers hardness of 300 to 500 HV, and secures sufficient strength.

This is for a conventional printed circuit board (PCB) that requires a process of manufacturing or plating a very thin copper foil of 15 μm or less, and requires additional processes such as heat treatment to supplement the bonding force between the copper foil and a metal layer plated thereon. It can be seen that it is a very advanced technology compared to the multi-layer metal thin film manufacturing method.

In addition, the present invention can prevent oxygen gas from being generated during the formation of the metal layer by providing the second cathode material as a soluble copper (Cu) metal ball. Through this, the quality of the metal layer can be improved.

Finally, the present invention independently controls process conditions such as type, concentration, and current density of the electrolyte supplied to each of the electrolytic cells 400a, 400b, 400c, 400d... in the plurality of electrolytic cells 400. It is possible to diversify the electrical, physical and mechanical properties of the metal thin film by providing Through this, single- or multi-layer metal thin films can be manufactured, and electrical, physical and mechanical properties can be diversified according to each part of the metal thin film.

In the above, the present invention has been described in detail using preferred embodiments, but the scope of the present invention is not limited to specific embodiments, and should be interpreted according to the appended claims. In addition, those skilled in the art should understand that many modifications and variations are possible without departing from the scope of the present invention.

100: multilayer metal thin film
110: first plating layer
130: metal layer
150: second plating layer
170: third plating layer
200: cathode rotating plate
400: electrolysis cell
1000: multi-layer metal thin film manufacturing device

Claims (13)

a first plating layer;
a metal layer containing copper formed on an upper surface of the first plating layer;
a second plating layer formed on an upper surface of the metal layer; and
Including a third plating layer formed on the upper surface of the second plating layer
The first plating layer, the metal layer, the second plating layer and the third plating layer are sequentially plated on one cathode rotating plate using an electroforming method, the multi-layer metal thin film. According to claim 1,
The multilayer metal thin film,
the cathode rotating plate; and
A multi-layer metal thin film, characterized in that it is manufactured by a multi-layer metal thin film manufacturing apparatus including the cathode rotating plate and first to fourth electrolytic cells for electroforming. According to claim 2,
The first to fourth electrolytic cells are disposed spaced apart from each other by a predetermined distance on one of the cathode rotating plates,
As the cathode rotating plate rotates, the first to fourth electrolytic cells are produced by a multi-layer metal thin film manufacturing apparatus in which electroforming is performed simultaneously with the cathode rotating plate. According to claim 1,
Characterized in that the first plating layer and the second plating layer are made of any one metal selected from the group consisting of nickel (Ni), cobalt (Co), tin (Sn), zinc (Zn) and iron (Fe), multilayer metal film. According to claim 1,
The first plating layer has a thickness of 0.5 to 5 μm,
The multi-layer metal thin film, characterized in that the thickness of the second plating layer is formed to 1 to 10㎛. According to claim 1,
Characterized in that the metal layer is provided as an electrolytic copper foil layer, a multi-layer metal thin film. According to claim 1,
The third plating layer is a multilayer metal thin film, characterized in that made of any one of gold (Au), silver (Ag), palladium (Pd) platinum (Pt) and aluminum (Al). In the method of manufacturing a multi-layer metal thin film in which a first plating layer, a metal layer, a second plating layer, and a third plating layer are sequentially plated on a cathode rotating plate,
charging the cathode rotating plate;
forming a first plating layer on an upper surface of the cathode rotating plate;
forming a metal layer on an upper surface of the first plating layer;
forming a second plating layer on an upper surface of the metal layer;
forming a third plating layer on an upper surface of the second plating layer; and
Including; peeling the prepared multi-layer metal thin film;
As the cathode rotating plate rotates, the first plating layer, the metal layer, the second plating layer and the third plating layer are electroformed at the same time, characterized in that, the method of manufacturing a multi-layer metal thin film. According to claim 8,
The manufacturing method of the multi-layer metal thin film, characterized in that the step of sealing the metal thin film between the step of forming the third plating layer and the step of peeling the multi-layer metal thin film is further included. According to claim 8,
The multilayer metal thin film,
the cathode rotating plate; and
Characterized in that it is manufactured by a multi-layer metal thin film manufacturing apparatus including the cathode rotary plate and the first to fourth electrolytic cells for electroforming, the method of manufacturing a multi-layer metal thin film. According to claim 10,
The first plating layer is
Formed by injecting a first electrolyte solution into the first electrolysis cell and then passing a first current;
The method of manufacturing a multi-layer metal thin film, characterized in that the first cathode material included in the first electrolysis cell is provided as a soluble nickel (Ni) metal piece. According to claim 10,
The metal layer,
Formed by injecting a second electrolyte into the second electrolysis cell and then passing a second current;
The method of manufacturing a multi-layer metal thin film, characterized in that the second cathode material included in the second electrolysis cell is provided as a soluble copper (Cu) metal ball. According to claim 10,
The third plating layer,
Formed by injecting a fourth electrolyte solution into the fourth electrolytic cell and then passing a fourth current;
The fourth anode material included in the fourth electrolytic cell is provided as a titanium (Ti) plate coated with iridium oxide (Ir ₂ O ₃ ).

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